EP2695864A1 - Laminiertes glas und verfahren zu seiner herstellung - Google Patents

Laminiertes glas und verfahren zu seiner herstellung Download PDF

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Publication number
EP2695864A1
EP2695864A1 EP12767308.5A EP12767308A EP2695864A1 EP 2695864 A1 EP2695864 A1 EP 2695864A1 EP 12767308 A EP12767308 A EP 12767308A EP 2695864 A1 EP2695864 A1 EP 2695864A1
Authority
EP
European Patent Office
Prior art keywords
glass
plate
mass
glass plate
thick
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP12767308.5A
Other languages
English (en)
French (fr)
Other versions
EP2695864A4 (de
EP2695864B1 (de
Inventor
Masahiro Tsuchiya
Yasumasa Kato
Yutaka Kitajima
Masashi KASAJIMA
Shuichi Akada
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
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Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Publication of EP2695864A1 publication Critical patent/EP2695864A1/de
Publication of EP2695864A4 publication Critical patent/EP2695864A4/de
Application granted granted Critical
Publication of EP2695864B1 publication Critical patent/EP2695864B1/de
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Anticipated expiration legal-status Critical

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06—Joining glass to glass by processes other than fusing
    • C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10082—Properties of the bulk of a glass sheet
    • B32B17/10119—Properties of the bulk of a glass sheet having a composition deviating from the basic composition of soda-lime glass, e.g. borosilicate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10889—Making laminated safety glass or glazing; Apparatus therefor shaping the sheets, e.g. by using a mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J1/00—Windows; Windscreens; Accessories therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J1/00—Windows; Windscreens; Accessories therefor
    • B60J1/008—Windows; Windscreens; Accessories therefor of special shape, e.g. beveled edges, holes for attachment, bent windows, peculiar curvatures such as when being integrally formed with roof, door, etc.
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/02—Re-forming glass sheets
    • C03B23/023—Re-forming glass sheets by bending
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/02—Re-forming glass sheets
    • C03B23/023—Re-forming glass sheets by bending
    • C03B23/025—Re-forming glass sheets by bending by gravity
    • C03B23/0252—Re-forming glass sheets by bending by gravity by gravity only, e.g. sagging
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/02—Re-forming glass sheets
    • C03B23/023—Re-forming glass sheets by bending
    • C03B23/025—Re-forming glass sheets by bending by gravity
    • C03B23/0256—Gravity bending accelerated by applying mechanical forces, e.g. inertia, weights or local forces
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/20—Uniting glass pieces by fusing without substantial reshaping
    • C03B23/203—Uniting glass sheets
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B40/00—Preventing adhesion between glass and glass or between glass and the means used to shape it, hold it or support it
    • C03B40/02—Preventing adhesion between glass and glass or between glass and the means used to shape it, hold it or support it by lubrication; Use of materials as release or lubricating compositions
    • C03B40/033—Means for preventing adhesion between glass and glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24628—Nonplanar uniform thickness material

Definitions

  • the present invention relates to laminated glass and its production process.
  • the two glass plates have the same glass composition and the same plate thickness from the viewpoint of the cost.
  • the interlayer is constituted by a resin such as polyvinyl butyral (PVB) and prevents the broken glass from flying.
  • a forming method of bending glass plates into a predetermined shape commonly employed is a gravity forming method of placing the glass plates on a ring-shape lower mold (ring mold) supporting the glass plates from below and passing them through a heating furnace to heat and soften the glass plates and bend the glass plates by gravity into shape along the ring mold.
  • a pressing method of sandwiching the glass plates preliminarily formed by gravity between the ring mold and a press mold, followed by pressing for main forming may also be employed.
  • Patent Document 1 proposes to make the glass plate on the car exterior side thicker than the glass plate on the car interior side, considering a collision of flying objects such as small stones from outside with the automobile.
  • Window glass for an automobile is formed in a convex curved shape toward the car exterior side at the time of attachment to a vehicle.
  • a thick glass plate and a thin glass plate are overlaid in this order on the ring mold, followed by heating and softening to bend them into a downwardly convex shape.
  • the thin glass plate is likely to deform and sag down as compared with the thick glass plate, and the following problems (1) and (2), etc. may arise.
  • laminated glass having glass plates differing in the plate thickness is problematic in the quality and the cost.
  • the object of the present invention is to provide laminated glass excellent in the quality and the cost and its production process capable of easily bending glass plates differing in the plate thickness with good accuracy, whereby the glass plates and the interlayer are sufficiently pressure bonded in the pressure bonding step and in addition, distortion of the glass plates is reduced.
  • the present invention provides laminated glass comprising a plurality of glass plates bent into a predetermined shape, and an interlayer interposed between the plurality of glass plates, at least two glass plates among the plurality of glass plates being a thick glass plate and a thin glass plate differing in the plate thickness; wherein at an any temperature between the annealing point and the softening point of the thick glass plate, the thick glass plate between the two glass plates differing in the plate thickness, has a lower viscosity than the thin glass plate.
  • a thicker glass plate will be referred to as a thick glass plate
  • a thinner glass plate will be referred to as a thin glass plate.
  • the present invention further provides a process for producing laminated glass, which comprises a forming step of heating a plurality of glass plates to the vicinity of the softening point and bending them into a predetermined shape; a lamination step of laminating the plurality of bent glass plates with an interlayer interposed therebetween; and a pressure bonding step of pressure bonding the laminated glass plates and the interlayer to form laminated glass; at least two glass plates among the plurality of glass plates constituting the laminated glass differing in the plate thickness; wherein at an any temperature between the annealing point and the softening point of the thick glass plate, the thick glass plate between the two glass plates differing in the plate thickness, has a lower viscosity than the thin glass plate.
  • the present invention it is possible to provide laminated glass excellent in the quality and the cost and its production process capable of easily bending glass plates differing in the plate thick with good accuracy, whereby distortion of the glass plates is reduced.
  • the type of glass plates of the laminated glass according to an embodiment of the present invention is soda lime glass, however, the type of the glass plates of the present invention is not limited, and for example, alkali-free glass may be employed.
  • the thin glass plate and the thick glass plate constituting the laminated glass according to this embodiment specifically preferably have the glass compositions according to the following first and second embodiments, as represented by mass% as calculated as oxides.
  • the thin glass plate is a soda lime glass plate having a composition comprising:
  • the thin glass plate is a glass plate having a composition comprising:
  • Al 2 O 3 is a component to secure the weather resistance, and its content is preferably at least 1.7 mass%, more preferably at least 1.8 mass%. Further, if it exceeds 4.0 mass%, the viscosity tends to be high, and melting may be difficult. From such a viewpoint, it is more preferably at most 3.5 mass%, particularly preferably at most 3.3 mass%.
  • Na 2 O is a component to improve the melting property, and if its content is lower than 12.6 mass%, the melting property may be decreased. It is more preferably at least 12.8 mass%, particularly preferably at least 13.0 mass%. Further, if it exceeds 15.0 mass%, the weather resistance may be decreased. It is more preferably at most 14.8 mass%, particularly preferably at most 13.8 mass%.
  • K 2 O is a component to improve the melting property, and its content is preferably at least 0.5 mass%, more preferably at least 0.9 mass%. Further, if it exceeds 2.0 mass%, the weather resistance may be decreased, and the cost of the glass plate will be high. It is more preferably at most 1.8 mass%, particularly preferably at most 1.6 mass%.
  • the soda lime glass plate according to the above first embodiment means a glass plate made of soda lime glass containing SiO 2 , CaO, Na 2 O and K 2 O as the main components, containing at least from 65 to 75 mass% of SiO 2 and from 7 to 14 mass% of CaO, and further containing Al 2 O 3 , Na 2 O and K 2 O within the above ranges.
  • Figs. 1 and 2 are views illustrating a process for producing laminated glass according to an embodiment of the present invention.
  • Fig. 1 is a view illustrating the forming step, and is a longitudinal cross section illustrating a heating furnace.
  • Fig. 2 is a view illustrating the lamination step.
  • Fig. 3 is a side view illustrating a glass laminate according to an embodiment of the present invention.
  • Fig. 4 is a side view illustrating laminated glass according to an embodiment of the present invention.
  • the process for producing laminated glass comprises a forming step, a lamination step and a pressure bonding step, at least two glass plates among a plurality of glass plates constituting the laminated glass differing in the plate thickness.
  • the plate thickness and the glass composition of each of the plurality of glass plates and the plate thickness ratio of the plurality of glass plates do not substantially change as between before and after the respective steps such as the forming step.
  • the forming step is a step of heating the plurality of glass plates differing in the plate thickness to the vicinity of the softening point of a glass plate having a higher softening point i.e. a thinner glass plate and bending them to a predetermined shape.
  • a gravity forming method is employed wherein the glass plates are placed on a ring mold and passed through a heating furnace to heat and soften them whereby to bend them into a predetermined shape by gravity.
  • a press forming method of sandwiching the glass plates preliminarily formed by gravity between the ring mold and a press mold, followed by pressing for main forming may also be employed.
  • a method may also be employed wherein glass plates heated to a predetermined temperature while being horizontally transferred on a plurality of rolls provided in the heating furnace are lifted up by the ring mold and brought close to a bending mold to form them into a shape along the bending mold.
  • a release agent is applied to place a plurality of glass plates 2 and 4 overlaid via a release agent on a ring mold 20 and bend them simultaneously.
  • the plurality of glass plates 2 and 4 placed on the ring mold 20 are arranged one above the other, and between the adjacent glass plates, a release agent is applied.
  • the release agent is to separate the adjacent glass plates so that they are easily separated from each other after forming.
  • a ceramic powder or the like which will not react with the glass plate or which will not melt at high temperature may be suitably used.
  • the plurality of glass plates 2 and 4 placed on the ring mold 20 in the gravity forming method include two glass plates differing in the plate thickness, and the thicker glass plate may be disposed on the lower side. In a case where three or more glass plates are placed on the ring mold 20, and there may be glass plates having the same plate thickness, the glass plates having the same plate thickness are disposed adjacent to each other.
  • the thinner glass plate may be disposed on the lower side.
  • vertical disposition of bent glass plates 12 and 14 is reversed and they are laminated, whereby it is possible to prevent irregularities on the glass plate 14 due to contact with the ring mold 20 from being exposed to the outside.
  • optimum forming procedure can be selected in accordance with bendability of the plurality of glass plates.
  • the release agent is unnecessary.
  • the ring 20 is a supporting mold formed into a ring-shape, which supports the plurality of (for example, two) glass plates 2 and 4 from below.
  • the ring mold 20 is guided in a predetermined direction along a rail in the interior of the heating furnace 30.
  • the interior of the heating furnace 30 is compartmentalized into a plurality of zones such as a pre-heating zone 32 of pre-heating the glass plates, a forming zone 34 of bending the glass plates and an annealing zone 36 of annealing the glass plates.
  • a heater or the like is provided so as to control the temperature in each zone.
  • the ring mold 20 passes through the pre-heating zone 32, the forming zone 34 and the annealing zone 36 in this order.
  • the temperature in the forming zone 34 is set to a temperature (usually from 550 to 650°C) suitable for bending of the glass plates, and in the forming zone 34, the glass plates are bent into a shape along the ring mold 20.
  • the ring mold 20 is formed into a frame-shape, and supports the periphery of the glass plates.
  • the ring mold 20 may be a unit or may be divided in a circumferential direction. In the latter case, a plurality of divided peaces constituting the ring mold may relatively be moved or moved rotationally as the case requires to obtain a predetermined shape. Further, rings partially differing in the curvature are overlaid in parallel with each other, and the supporting rings may be changed in accordance with the degree of bending of the glass plate.
  • the plurality of flat glass plates 2 and 4 are bent to obtain a plurality of glass plates 12 and 14 having a predetermined shape.
  • the obtained plurality of glass plates 12 and 14 are sufficiently cooled and cleaned as the case requires (for example, to remove the release agent) and then subjected to a lamination step.
  • the lamination step is a step of laminating the plurality of bent glass plate 12 and 14 with an interlayer 40 interposed therebetween, as shown in Fig. 2 .
  • a glass laminate (non-pressure bonded product) 50 is obtained as shown in Fig. 3 .
  • the glass laminate 50 includes the two glass plates 12 and 14 differing in the plate thickness.
  • the glass laminate means a non-pressure bonded laminated before the pressure bonding step, in a state where the plurality of glass plates are laminated with an interlayer interposed therebetween, and is distinguished from the laminated glass obtained by the pressure bonding step.
  • the interlayer 40 is constituted by a resin such as polyvinyl butyral (PVB), and is interposed between the adjacent glass plate 12 and 14.
  • the interlayer 40 prevents the broken glass from flying, when the after-mentioned laminated glass 60 is broken.
  • a plurality of (for example, two) glass plates 12 and 14 in conformity with each other in the shape may be selected among the plurality of bent glass plates and laminated.
  • the plurality of glass plates 12 and 14 simultaneously bent on one ring mold 20 may be respectively pressure bonded with glass plates of a different pair to prepare laminated glass.
  • the two glass plates 12 and 14 to be laminated are preferably laminated so that the concave curved surface of the glass plate 12 having a large radius of curvature and the convex curved surface of the glass plate 14 having a small radius of curvature face each other.
  • the convex curved shape means a protruded curved surface of a glass plate
  • the concave curved surface means a dent curved surface of a glass plate. The difference in the radius of curvature between the two glass plates 12 and 14 is slight.
  • the plurality of glass plates 12 and 14 differing in the plate thickness are horizontally arranged and laminated so that the thicker glass plate is disposed closer to the convex curved surface of the glass laminate 50, whereby when laminated glass 60 is attached to a vehicle body as window glass for an automobile, the thicker glass plate is disposed closer to the car exterior side, whereby durability against impact from the car exterior e.g. by flying stones can be improved.
  • the pressure bonding step is a step of pressure bonding the laminated glass plates 12 and 14 and the interlayer 40 to form laminated glass 60 as shown in Fig. 4 .
  • the laminated glass 60 is obtained by putting the glass laminate 50 obtained in the lamination step into an autoclave, followed by heating and pressure bonding, and has a predetermined bent shape.
  • the process for producing laminated glass may further has a formation step of forming a functional material layer 8 (see Fig. 1 ) on the surface of the glass plate, in addition to the above forming step, lamination step and pressure bonding step.
  • the functional material is not particularly limited and may, for example, be an electrically conductive material such as a metal material or a decorating material such as a heat resistant pigment.
  • an ink containing a binder and a solvent in addition to the functional material is applied to the surface of the glass plate and dried to form the functional material layer 8.
  • a plural types of functional material layers 8 may be formed on the surface of one glass plate.
  • the functional material layer 8 is formed in a predetermined pattern.
  • the formation step may be carried out prior to the forming step, and in such a case, the ink can be applied to the surface of flat glass, whereby good coating operation property is obtained.
  • the method of applying the ink for example, a screen printing method, a die coating method or the like may be mentioned.
  • the functional material layer 8 when fired is baked on the surface of the glass plate to form a functional film 18 (see Fig. 1 ) containing the functional material.
  • the functional film 8 may, for example, be an electrically conductive film or electrically conductive striae containing an electrically conductive material, and constitutes e.g. an antenna receiving electrical radiation for TV broadcasting, AM/FM broadcasting or PHS, heat electric wire for anti-icing or the like.
  • the functional film 18 may be a decorating film containing a decorating material, which contains a heat resistant black pigment, and restricts visibility from outside or restricts transmission of sunlight.
  • At least two glass plates 12 and 14 among the plurality of glass plates 12 and 14 constituting the laminated glass 60 have different plate thicknesses.
  • the laminated glass shown in Figs. 3 and 4 as an example is laminated glass having two glass plates, and the two glass plates 12 and 14 (i.e. glass plates 2 and 4) differing in the plate thickness have different viscosities, and at an any temperature between the annealing point and the softening point of the thick glass plate 12, the thick glass plate 12 has a lower viscosity than the thin glass plate 14.
  • the annealing point means a temperature at which the viscosity of glass becomes 10 13 dPa ⁇ s, and is determined e.g. by the composition of glass.
  • the annealing point of soda lime glass is typically about 550°C. At a temperature lower than the annealing point, the glass plate undergoes substantially no heat deformation.
  • the softening point means a temperature at which the viscosity of glass becomes 10 7.65 dPa ⁇ s and is determined e.g. by the composition of glass.
  • the softening point of soda lime glass is typically about 750°C.
  • the bending temperature of the glass plate is set to the same temperature as the softening point or a temperature slightly lower than the softening point.
  • the viscosity of glass depends on e.g. the composition of glass and the ⁇ -OH value (mm -1 ) indicating the moisture content, at the same glass temperature.
  • the ⁇ -OH value (mm -1 ) indicating the moisture content, at the same glass temperature.
  • the ⁇ -OH value (mm -1 ) is an index of the moisture content in glass, and the ⁇ -OH value of glass can be obtained by measuring the absorbance of a glass sample to light having a wavelength of from 2.75 to 2.95 ⁇ m, and dividing its maximum ⁇ max by the thickness (mm) of the sample.
  • the ⁇ -OH value (mm -1 ) of a glass plate varies depending upon the amount of moisture in the material, the type (e.g. fuel oil, LNG or electricity) of a heat source for melting the material, the water vapor concentration in a melting tank, the retention time of molten glass in the melting tank, etc., and is preferably adjusted by a method of using a hydroxide instead of an oxide as the glass material (for example, magnesium hydroxide (Mg(OH) 2 ) is used instead of magnesium oxide (MgO) as a magnesium source).
  • the moisture content in the glass plate is from 0.1 to 0.4 by the ⁇ -OH value (mm -1 ), preferably from 0.2 to 0.3.
  • the viscosity of glass is lower as the temperature of glass increases, with the same glass composition.
  • the viscosity of glass is represented by the following formula (1) with the same glass composition.
  • ⁇ is the viscosity (dPa ⁇ s) of glass
  • T is the temperature (°C) of glass.
  • A, ⁇ 0 (dPa ⁇ s), B (°C) and To (°C) are respectively constants determined e.g. by the composition of glass.
  • Fig. 5 is a graph schematically illustrating the relation between the viscosity and the temperature of glass calculated based on Fulcher formula.
  • the vertical axis represents the logarithm (to base 10) of the viscosity ⁇ of glass
  • the horizontal axis represents the temperature T of glass. As shown in Fig. 5 , with the same composition of glass, the higher T is, the lower ⁇ is.
  • the viscosity of glass at a predetermined temperature is measured by a so-called beam bending method (hereinafter referred to as "BB method").
  • the BB method is a measuring method suitable for measuring the viscosity at a predetermined temperature between the annealing point and the softening point.
  • Fig. 6 is a view illustrating measurement of the viscosity by BB method.
  • a three-point bending testing machine 100 is employed for the viscosity measurement by BB method.
  • the rate of deflection means the displacement rate in the vertical direction.
  • ⁇ is the viscosity (dPa ⁇ s) of glass
  • G is the gravitational acceleration (cm/sec 2 )
  • L is the distance (cm) between the two support points
  • I is the cross-sectional second moment (cm 4 ) of the test piece
  • v is the rate of deflection (cm/min) at the center portion of the test piece
  • M is the load (g) applied to the center portion in the longitudinal direction of the test piece
  • ⁇ is the density (g/cm 3 ) of glass
  • S is the cross section (cm 2 ) of the test piece.
  • the two glass plates 12 and 14 i.e. glass plates 2 and 4) differing in the plate thickness have different glass viscosities, and at an any temperature between the annealing point and the softening point of the thick glass plate 12, the thick glass plate 12 has a viscosity lower than the thin glass plate 14. Accordingly, the difference in the plate thickness can be compensated by the difference in the viscosity, and the two glass plates 12 and 14 differing in the plate thickness can easily be bent with good accuracy.
  • the total deflection amount of the test piece 110 may be employed, which is obtained by heating the test piece 110 from 400°C to 630°C in a state where a certain load (50 gf) is applied to the test piece 110 having a plate thickness t (mm) using the three-point bending test machine 100 shown in Fig. 6 .
  • This total amount of deflection D (cm) is calculated from the following formula (4).
  • the heating start temperature of the test piece 110 is set at 400°C because the heat deformation of the test piece is negligibly small at a temperature of 400°C or below.
  • T is the temperature of the test piece.
  • E is the heating rate (°C/min) of the test piece from 400°C to 630°C and is 10 (°C/min).
  • the formula (5) is obtained by substituting the formula (1) in the formula (3), and L and I are determined e.g. by t. L and I are values at room temperature, since their temperature dependence is negligibly small.
  • x is the plate thickness ratio of the two test pieces
  • the values of y and z are calculated by substituting ⁇ T and the like shown in Table 1 into the formula (4) (the formula (5) in detail)).
  • the values A and B are constant and To alone is adjusted as mentioned above, since the dependence of A and B on the glass composition is small as compared with To.
  • the value x represents the ratio (t2/t1) of the plate thickness (t2) of the thin test piece to the plate thickness (t1) of the thick test piece at room temperature.
  • the value y represents the ratio (log 10 ⁇ 2 /log 10 ⁇ 1 ) of the logarithm (log 10 ⁇ 2 ) of the viscosity of the thin test piece to the logarithm (log 10 ⁇ 1 ) of the viscosity of the thick test piece at the annealing point of the thick test piece.
  • the value z represents the ratio (log 10 ⁇ 4 /log 10 ⁇ 3 ) of the logarithm (log 10 ⁇ 4 ) of the viscosity of the thin test piece to the logarithm (log 10 ⁇ 3 ) of the viscosity of the thick test piece at the softening point of the thick test piece.
  • the two glass plates 12 and 14 i.e. glass plates 2 and 4) differing in the plate thickness preferably satisfy the following formulae (6) and (7) so that they are in conformity with each other in the bendability in the forming step.
  • x, y and z have the same meanings as in Table 1, and x is the plate thickness ratio of the two glass plates 12 and 14 at room temperature, y is the ratio of the logarithms of the viscosities of the two glass plates 12 and 14 at the annealing point of the thick glass plate 12, and z is the ratio of the logarithms of the viscosities of the two glass plates 12 and 14 at the softening point of the thick glass plate 12.
  • the bending amount of the thick glass plate is larger than the bending amount of the thin glass plate in the forming step. Accordingly, if the two glass plates are laminated so that the concave curved surface of the thick glass plate and the convex curved surface of the thin glass plate face each other, pressure bonding failure is likely to occur between the two glass plates.
  • b 1 is preferably 1.21, more preferably 1.20.
  • c 1 is preferably 1.14, more preferably 1.13.
  • the two glass plates differing in the plate thickness more preferably satisfy the following formulae (8) and (9), in addition to the above formulae (6) and (7).
  • the formula (8) is effectively employed only when x is small to a certain extent, and specifically, effectively employed only when 1 ⁇ b 2 -0.206 ⁇ x.
  • the formula (9) is effectively employed only when x is small to a certain extent, and specifically, effectively employed only when 1 ⁇ c 2 -0.131 ⁇ x b 2 - 0.206 ⁇ x ⁇ y c 2 - 0.131 ⁇ x ⁇ z
  • b 2 is preferably 1.12, more preferably 1.13.
  • c 2 is preferably 1.07, more preferably 1.08.
  • Fig. 9 is a graph illustrating the relation between x and y which satisfy the formulae (6) and (8).
  • a region where the formulae (6) and (8) are satisfied is indicated by oblique lines.
  • the relation between x and y shown in Table 1 is plotted.
  • the formula (8) is effectively on when x is small to a certain extent.
  • Fig. 10 is a graph illustrating the relation between x and z which satisfy the formulae (7) and (9).
  • the region where the formulae (7) and (9) are satisfied is indicted by oblique lines.
  • the relation between x and z shown in Table 1 is plotted.
  • the formula (9) is effective only when x is small to a certain extent.
  • the two glass plates 12 and 14 i.e. glass plates 2 and 4) differing in the plate thickness preferably satisfy the formula 0.3 ⁇ x ⁇ 0.9.
  • the laminated glass 60 can be made sufficiently thin while the strength and the resistance to flying stones of the thick glass plate 12 (the glass plate on the car exterior side) are maintained.
  • the strength of the thin glass plate 14 can sufficiently be secured.
  • 0.3 ⁇ x ⁇ 0.76 is more preferred, and 0.33 ⁇ x ⁇ 0.66 is further preferred.
  • the plate thickness of the glass plate to be disposed on the car exterior side of the laminated glass is preferably thicker than 1.6 mm, more preferably at least 1.8 mm. Further, the plate thickness of the glass plate to be disposed on the car interior side is preferably thinner than 1.6 mm, more preferably thinner than 1.3 mm, particularly preferably thinner than 1.1 mm. On the other hand, when it is thicker than 0.7 mm, the handling of the glass plate tends to be easy, and when it is thicker than 1 mm, the compatibility with the existing equipment for production of window glass for an automobile tends to be high, such being favorable.
  • the plate thickness difference between the thick plate and the thin plate is preferably at least 0.5 mm, more preferably at least 0.65 mm, whereby weight saving is possible while the strength and the resistance to flying stones are secured.
  • the value y is preferably 1.017 ⁇ y, more preferably 1.02 ⁇ y, further preferably 1.03 ⁇ y.
  • the laminated glass 60 is window glass for a vehicle, and as shown in Fig. 4 for example, the number of the glass plates 12 and 14 constituting the laminated glass 60 may be two, and the convex curved surface of the laminated glass 60 is constituted by the convex curved surface of the thick glass plate 12.
  • the thick glass plate 12 is disposed on the car exterior side, whereby the laminated glass 60 is less likely to be broken when flying objects such as small stones from outside collide with the automobile.
  • the laminated glass has two glass plates, however, it may have three or more glass plates so long as two glass plates in the laminated glass have different plate thicknesses.
  • the other glass plate other than the two glass plates may have a plate thickness different from both of the two glass plates, or may have the same plate thickness as one of them.
  • the two glass plates are preferably such that the thick glass plate has a lower viscosity than the thin glass plate at an optional temperature between the annealing point and the softening point of the thick glass plate.
  • the glass plates having the same plate thickness preferably have the same glass viscosity.
  • Example 1 two flat glass plates (soda lime glass) are prepared.
  • the two glass plates have different plate thicknesses, the thick glass plate has a plate thickness of 2.0 mm, and the thin glass plate has a plate thickness of 1.1 mm. Further, the two glass plates have different compositions, and as a result of analysis of the composition of each glass plate by fluorescent X-ray analysis, the thick glass plate has a Na 2 O content higher than that of the thin glass plate.
  • an ink obtained by mixing glass flit, a heat resistant black pigment and an organic vehicle is applied and dried to form a decorating material layer.
  • the glass plate having a thickness of 2.0 mm and the glass plate having a thickness of 1.1 mm are overlaid in this order on a ring mold as shown in Fig. 1 so that the decorating material layer is disposed on the upper side of the thin glass plate.
  • a release agent containing a ceramic powder is applied between the two glass plates.
  • the ring mold on which the two glass plates are overlaid is moved from an inlet of a heating furnace to a forming zone via a pre-heating zone, whereby the softened two glass plates are bent into a shape along the ring mold by gravity and in addition, the decorating material layer is subjected to heat treatment for removal of the binder and then fired to form a decorating film.
  • the convex curved surface of the thin glass plate and the concave curved surface of the thick glass plate face each other.
  • the ring mold is moved from the forming zone to the annealing zone and then discharged from the outlet of the heating furnace.
  • the two glass plates are sufficiently cooled, and they are taken out from the ring mold, the release agent is removed by cleaning, and the outer appearance of each glass plate is visually observed. As a result, no defect resulting from irregularities due to the ceramic powder contained in the release agent is confirmed, and there is no problem in the visual quality.
  • the concave curved surface of the thick glass plate and the convex curved surface of the thin glass plate are disposed to face each other, and the two glass plates are laminated with an interlayer comprising polyvinyl butyral (PVB) interposed therebetween to form a glass laminate (non-pressure bonded product).
  • the glass laminate is heated and pressure bonded in an autoclave to obtain laminated glass having a predetermined bent shape.
  • the obtained laminated glass is visually observed, whereupon no pressure bonding failure between the adjacent glass plates is observed, and no crack is confirmed.
  • Example 2 laminated glass is prepared in the same manner as in Example 1 except that the plate thickness of the thin glass plate is 1.6 mm, and the glass composition of the thin glass plate is changed.
  • the viscosities at a plurality of temperatures are obtained by BB method as shown in Fig. 6 , and A, B and To in the formula (1) are determined by the least-squares method so that the difference with the formula (1) as the model formula becomes smallest.
  • the two glass plates are sufficiently cooled, and they are taken out from the ring mold, the release agent is removed by cleaning, and the outer appearance of each glass plate is visually observed. As a result, no defect resulting from irregularities due to the ceramic powder contained in the release agent is confirmed, and there is no problem in the visual quality.
  • the obtained laminated glass is visually observed, whereupon no pressure bonding failure between the adjacent glass plates is observed, and no crack is confirmed.
  • Example 3 laminated glass is prepared in the same manner as in Example 1 except that the compositions of the thin glass plate and the thick glass plate are changed as identified in Table 3.
  • the two glass plates are sufficiently cooled, and they are taken out from the ring mold, the release agent is removed by cleaning, and the outer appearance of each glass plate is visually observed. As a result, no defect resulting from irregularities due to the ceramic powder contained in the release agent is confirmed, and there is no problem in the visual quality.
  • the obtained laminated glass is visually observed, whereupon no pressure bonding failure between the adjacent glass plates is observed, and no crack is confirmed.
  • Example 4 laminated glass is prepared in the same manner as in Example 1 except that the compositions of the thin glass plate and the thick glass plate are changed as identified in Table 3.
  • the two glass plates are sufficiently cooled, and they are taken out from the ring mold, the release agent is removed by cleaning, and the outer appearance of each glass plate is visually observed. As a result, no defect resulting from irregularities due to the ceramic powder contained in the release agent is confirmed, and there is no problem in the visual quality.
  • Comparative Example 1 laminated glass is prepared in the same manner as in Example 1 except that the glass composition of the thin glass plate is changed to be the same as the glass composition of the thick glass plate.
  • the two glass plates are sufficiently cooled, and they are taken out from the ring mold, the release agent is removed by cleaning, and the outer appearance of each glass plate is visually observed. As a result, defects resulting from irregularities due to the ceramic powder contained in the release agent are observed, and a perspective distortion is observed.
  • the obtained laminated glass is visually observed, whereupon pressure bonding failure between the adjacent glass plates is confirmed, and cracks are also confirmed.
  • the present invention it is possible to provide laminated glass excellent in the quality and the cost and its production process capable of easily bending glass plates differing in the plate thickness with good accuracy, whereby the distortion of the glass plates is reduced, and the laminated glass of the present invention is particularly useful as laminated glass for an automobile.

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EP12767308.5A 2011-04-01 2012-04-02 Laminiertes glas und verfahren zu seiner herstellung Active EP2695864B1 (de)

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US11420900B2 (en) 2018-09-26 2022-08-23 Apple Inc. Localized control of bulk material properties
CN109265023B (zh) * 2018-09-26 2020-02-21 福耀玻璃工业集团股份有限公司 一种非对称厚度的夹层玻璃及其制造方法
CN113272134A (zh) * 2018-11-30 2021-08-17 康宁公司 用于使用分离粉末形成非对称玻璃层板的方法和由所述方法制成的层板
US11680010B2 (en) 2019-07-09 2023-06-20 Apple Inc. Evaluation of transparent components for electronic devices
EP3771695A1 (de) 2019-07-31 2021-02-03 Corning Incorporated Verfahren und system zur kaltumformung von glas
US20240083143A1 (en) * 2019-10-18 2024-03-14 Corning Incorporated System and process for forming curved glass laminate article using separation material
CN114901474A (zh) * 2019-10-30 2022-08-12 康宁公司 用于压弯两个或更多个玻璃层的方法和系统
CN115955798A (zh) 2020-03-28 2023-04-11 苹果公司 用于电子设备壳体的玻璃覆盖构件
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EP2722318A4 (de) * 2011-06-20 2015-03-11 Asahi Glass Co Ltd Verfahren zur herstellung von beschichtetem glas und beschichtetes glas
EP2905267A4 (de) * 2012-10-02 2016-08-17 Asahi Glass Co Ltd Verfahren zur herstellung von beschichtetem glas
FR3012072A1 (fr) * 2013-10-23 2015-04-24 Saint Gobain Verre feuillete mince pour pare-brise
WO2015059407A1 (fr) * 2013-10-23 2015-04-30 Saint-Gobain Glass France Verre feuillete mince pour pare-brise
US10343378B2 (en) 2013-10-23 2019-07-09 Saint-Gobain Glass France Thin laminated glass for windscreen
US10960648B2 (en) 2017-01-12 2021-03-30 Central Glass Company, Limited Automotive laminated glass, and production method therefor
US11384013B2 (en) 2017-01-12 2022-07-12 Central Glass Company, Limited Automotive laminated glass, and production method therefor
EP3571046A4 (de) * 2017-01-20 2020-10-14 Pittsburgh Glass Works, LLC Asymmetrische schichtverglasung mit hoher schlagzähigkeit
US11465927B2 (en) 2017-02-20 2022-10-11 Corning Incorporated Shaped glass laminates
US11987516B2 (en) 2017-02-20 2024-05-21 Corning Incorporated Shaped glass laminates
US11236003B2 (en) 2017-10-18 2022-02-01 Corning Incorporated Methods for controlling separation between glasses during co-sagging to reduce final shape mismatch therebetween
US11897804B2 (en) 2018-04-13 2024-02-13 Corning Incorporated Uniformly pair sagged glass articles and hybrid laminates

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EP2695864A4 (de) 2014-09-17
BR112013024972A2 (pt) 2017-03-21
CN103443045A (zh) 2013-12-11
KR20140012702A (ko) 2014-02-03
US9375900B2 (en) 2016-06-28
WO2012137742A1 (ja) 2012-10-11
US20140065374A1 (en) 2014-03-06
EP2695864B1 (de) 2019-07-03
RU2600946C2 (ru) 2016-10-27
RU2013148730A (ru) 2015-05-10
CN103443045B (zh) 2015-09-30
JP5929903B2 (ja) 2016-06-08
JPWO2012137742A1 (ja) 2014-07-28

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